-
Japan Advanced Institute of Science and Technology
JAIST Repositoryhttps://dspace.jaist.ac.jp/
Title
High proton conduction of organized sulfonated
polyimide thin films with planar and bent
backbones
Author(s)Ono, Yutaro; Goto, Ryosuke; Hara, Mitsuo; Nagano,
Shusaku; Abe, Takashi; Nagao, Yuki
Citation Macromolecules, 51(9): 3351-3359
Issue Date 2018-04-23
Type Journal Article
Text version author
URL http://hdl.handle.net/10119/15728
Rights
Yutaro Ono, Ryosuke Goto, Mitsuo Hara, Shusaku
Nagano, Takashi Abe, Yuki Nagao, Macromolecules,
2018, 51(9), pp.3351-3359. This document is the
unedited author's version of a Submitted Work
that was subsequently accepted for publication in
Macromolecules, copyright (c) American Chemical
Society after peer review. To access the final
edited and published work, see
http://dx.doi.org/10.1021/acs.macromol.8b00301
Description
-
1
High proton conduction of organized sulfonated
polyimide thin films with planar and bent
backbones
Yutaro Ono†, Ryosuke Goto‡, Mitsuo Hara‡,
Shusaku Nagano‡, Takashi Abe∥, Yuki Nagao†*
† School of Materials Science, Japan Advanced Institute of
Science and Technology, 1-
1 Asahidai, Nomi, Ishikawa 923-1292, Japan
‡ Department of Molecular Design & Engineering, Graduate
School of
Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya
464-8603, Japan
§ Nagoya University Venture Business Laboratory, Nagoya
University, Furo-cho,
Chikusa, Nagoya 464-8603, Japan
∥ Graduate School of Science and Technology, Niigata University,
8050 Ikarashi 2-no-
cho, Nishi-ku, Niigata 950-2181, Japan
*[email protected] (Y.N.), Phone: +81(Japan)-761-51-1541,
Fax: +81(Japan)-761-51-1149, Address: 1-1 Asahidai, Nomi,
Ishikawa 923-1292, Japan
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2
Abstract
Fast proton conduction was achieved in organized lamellar
structures with in-plane
oriented structure parallel to the substrate surface using a
lyotropic liquid-crystalline (LC)
property. Alkyl sulfonated polyimides (ASPIs) with bent main
chain structure were newly
synthesized to investigate relations between the higher order
structure and proton
transport properties. Proton conductivity of all polyimide thin
films was greater than 10-
2 S/cm-1. Grazing-incidence small-angle X-ray scattering
(GI-SAXS) revealed that both
planar and bent ASPI thin films exhibited humidity-induced
lyotropic lamellar structure.
Infrared p-polarized multiple-angle incidence resolution (pMAIR)
studies revealed that
main chain backbones of both planar and bent ASPI thin films
show an in-plane
orientation parallel to the substrate surface. Results
demonstrate that sulfonated alkyl side
chains contribute strongly to the lyotropic LC property, which
enhances molecular
orderings and proton conductivity by water uptake. This study
extends knowledge of the
molecular design for highly proton conductive polymers with
humidity-induced lyotropic
LC property.
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3
1. Introduction
Studies of energy conversion technology have expanded rapidly to
support the use of
next-generation power sources for sustainable energy. Polymer
electrolyte fuel cells have
been anticipated as ideal energy conversion systems because they
are environmentally
friendly and highly efficient systems for conversion from
chemical energy to electrical
energy. Great effort has been devoted to studies of advanced
polymer electrolytes because
they are important components of polymer electrolyte fuel
cells.1–5
To achieve high proton conductivity of polymer electrolytes,
various polymer
electrolyte membranes such as perfluorosulfonated polymers,6–9
sulfonated block
copolymers and graft copolymers have been examined based on a
concept of the well
phase-separated hydrophilic channels composed of hydrophobic
backbones and
hydrophilic parts. The proton conductivity of polymer
electrolyte membranes is closely
related to several parameters such as acidity, number of
sulfonic acid groups, main chain
and side chain structures, and membrane morphology.10–15 From a
different perspective,
structural confinement effects of polymer electrolyte thin films
have been reported.16–37
Structure and transport properties in confined polymer thin
films differ drastically from
those of the bulk materials because of interactions between the
polymer and substrate
surface.38,39 For example, a study of Nafion thin films
demonstrated that the degree of the
-
4
phase segregation, water uptake, and proton conductivity
decreased concomitantly with
decreasing film thickness. 26,34,35
Recent investigations have assessed structural controls of the
proton conductive
channels undertaken for the enhancement of proton conductive
properties.19–25 Sato and
Matsui et al. reported that the well-defined two-dimensional
lamellar structure of
Langmuir–Blodgett thin films shows high proton conductivity with
large anisotropic
proton conduction. 19–21 These results demonstrate the
possibility of proton conductivity
enhancement using the molecular orientation. Additionally,
several ion conductive liquid-
crystalline (LC) materials have been developed. Furthermore, the
relation between
molecular assembled nanostructures and transport properties has
been studied.40–49 These
materials comprise ionic liquids and thermotropic LC property.
These LC materials
exhibit interesting properties such as one-dimensional ion
transport, switching ionic
conductivity, and phase transition.
Our recent study has elucidated that proton conductivity
enhancement originates from
the molecular ordering and orientation of the LC-like domains of
alkyl sulfonated
polyimide (ASPI) thin films.22–24 Actually, ASPI exhibits a
lyotropic LC property by
water uptake because of their rigid aromatic backbones and
sulfonated alkyl side chains
holding an amphiphilic property. ASPI thin films with rigid and
planar molecular
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5
structure show a lamellar structure parallel to the substrate
surface, which expands
reversibly to the out-of-plane direction by water uptake.
Furthermore, the degree of the
molecular ordering improves by water uptake. The proton
conductivity improves by these
structural changes and exhibits more than 10-2 S/cm.22–24
Nevertheless, the role of
backbone rigidity and the side chain contribution for the
lyotropic LC property remains
unclear.
Ando and co-workers have investigated details of molecular
aggregation structures of
both fully aromatic and semialiphatic polyimides with no
sulfonated alkyl side chains.50
They found that the polyimide consisting of pyromellitic
dianhydride and 4,4-
diaminodiphenyl ether with nonplanar and bent molecular
structure includes a mixture of
the amorphous matrix and LC-like ordered domains. Steric effects
of the polyimide have
influenced the interchain packing structure. In other words,
different monomer structures
can modify such higher order structures of polyimides.
This work provides new insight into the relation between the
proton transport property
and organized polymer nanostructure. Herein, we synthesized four
humidity-induced
lyotropic LC polyimides consisting of planar and bent polymer
backbones with alkyl
sulfonated side chains. The origin of lyotropic LC property in
ASPI thin films was
elucidated from the viewpoint of main chain rigidity and side
chain effects. Grazing-
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6
incidence small-angle X-ray scattering (GI-SAXS) was used to
elucidate the organized
structure of thin films. In addition, infrared p-polarized
multiple-angle incidence
resolution (pMAIR) studies were conducted to reveal a molecular
orientation to the
substrate surface. AC impedance and water uptake by quartz
crystal microbalance (QCM)
were measured to quantify the proton conductivity. Both planar
and bent ASPI thin films
exhibited high proton conductivity and humidity-induced
lyotropic lamellar structure
parallel to the substrate plane. This study extends the
molecular design for highly proton
conductive polymers with humidity-induced lyotropic LC
property.
2. Experimental section
2-1. Materials
1,4,5,8-Naphthalenetetracarboxylic dianhydride (NTDA) was used
as received from
Sigma–Aldrich. 3,3′-Dihydroxybenzidine, 1,3-propanesultone,
pyromellitic dianhydride
(PMDA), 4,4'-oxydiphthalic dianhydride (ODPA), and
4,4'-biphthalic dianhydride
(BPDA) were used as received from TCI, Japan. Sodium hydroxide
(Kishida Chemical
Co. Ltd., Japan), hydrochloric acid (Nacalai Tesque Inc.,
Japan), m-cresol, and
triethylamine (TEA) (Kanto Chemical Co. Inc., Japan) were used
as received. Acetic acid,
acetic anhydride, methanol, and acetone were obtained from Wako
Pure Chemical
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7
Industries Ltd., Japan.
3,3'-Bis(sulfopropoxy)-4,4'-diaminobiphenyl (BSPA) was
synthesized according to previous reports22–24 (Scheme S1,
Figure S1).
Sulfonated polyimide with various molecular structures was
prepared using the same
polymerization scheme (Scheme 1). A typical synthesis for ASPI
is described as presented
below. 1 mmol of BSPA, 1 mmol of anhydride-monomer, 7 ml of
m-cresol, and 300 μl of
TEA were added to a round-bottom flask equipped with a magnetic
stirrer bar under argon
atmosphere at a constant temperature of 150°C for 6 h. The
polymerized product was
precipitated in large excess cooled acetone. The precipitate was
collected by centrifuge,
washed several times with fresh acetone, and dried under vacuum
overnight. The final
product was subjected to an ion-exchange process using
Amberlyst. 1H NMR
measurements were taken using a spectrometer (Bruker Avance III
400; Bruker Analytik
GmbH) using deuterated dimethyl sulfoxide used and
tetramethylsilane (TMS). Infrared
(IR) attenuated total reflection (ATR) spectra were measured
with a Fourier-transform
infrared (FTIR) spectrometer (Nicolet 6700; Thermo Fisher
Scientific Inc.) in the range
of 400−4000 cm-1.
The chemical structures of the synthesized ASPI by 1H NMR are
presented in Figure
S2. Peaks between δ = 7 to 9 ppm corresponded to the H atoms in
the aromatic rings. The
aliphatic protons were observed at δ = 2.0−4.4 ppm. Integration
of proton peaks in 1H
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8
NMR spectrum showed good agreement with the number of hydrogens
in both the
backbone and side chain of ASPI structure. No residual amide or
carboxylic protons were
noticed, which indicates that the imidization reaction was
complete. The spectrum was
observed after ion exchanged product: an extremely small amount
of the TEA was
observed. The calculated residual TEA was almost 1%. The
calculated ion exchange
capacity (IEC) values were estimated to be 2.86 (ASPI-1), 3.08
(ASPI-2), 2.69 (ASPI-3)
and 2.75 mequiv g-1 (ASPI-4) by 1H NMR results. The yields of
each polymer were 80%
(ASPI-1), 63% (ASPI-2), 68% (ASPI-3), and 85% (ASPI-4). FTIR-ATR
spectra of all
ASPIs are presented in Figure S3. The absorption bands of the
(C=O) were observed at
1720 and 1780 cm−1, which can be attributable as C=O asymmetric
and symmetric
stretching vibrations in ASPI-2, ASPI-3, and ASPI-4 cases.
Similar vibrations of the C=O
were observed at 1660 and 1710 cm−1 in ASPI-1. The observed
vibrational mode at 1500
cm−1 is attributed to the phenyl C−C stretching vibration. The
vibrational mode at 1380
(in ASPI-2, ASPI-3, ASPI-4) and 1350 (in ASPI-1) cm−1 is a C−N
bond of the imide
groups. The characteristic absorption bands of the sulfonic acid
groups (O=S=O)
normally appeared between 1030 cm−1 and 1250 cm−1. The molecular
weights (Mw) of
ASPI were ascertained using gel permeation chromatography (GPC).
This study selected
high molecular weight (ca. 5–8 ×105) ASPI samples.
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9
Scheme 1. Synthesis of sulfonated polyimide.
2-2. Gel Permeation Chromatography (GPC)
The molecular weights of ASPI were found using GPC (LC-2000plus;
Jasco Corp.) with
Shodex GF-1G 7B and GF-7M HG columns. An eluent was applied at a
flow rate of 1.0
mL min–1 using mixture of DMF, H2O, CH3COOH, and NaNO3. Before
injection of the
sample into the column, solutions were filtered through a 0.50
μmφ PTFE hydrophobic
filter. Polystyrene was used as a standard sample for molecular
weight.
NH2H2N
O O
SO3H SO3H
O O
O
O
O
O
R1
R1:
+m-cresol
TEA, 150℃
O
O
O
O
O
O
OO O
O
O
O
O
O O
O
O
O
O
O O
SO3H SO3H
nR2
N N
O
O
O
O
R2:N
O
O
N
O
O
ON N
O
O
O
O
N N
O
O
O
O
ASPI-1 ASPI-2
ASPI-3 ASPI-4
Ion-exchange
Planar backbone
Bent backbone
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10
2-3. Thin Film Preparation
For this study, Si, SiO2 substrates (each 15 × 15 × 0.5 mm) and
SiO2 -coated 9 MHz quartz
crystal microbalance (QCM) substrates (Seiko EG&G Co. Ltd.)
were used respectively
for thin films using spin-coating (ACT-200; Active Co. Ltd.),
few wt% ASPI dispersion
was used. Thicknesses of ca. 500 nm were found using an atomic
force microscope (AFM,
VN-8000; Keyence Co.) and a White interference microscope
(BW-S506; Nikon Corp.).
The ASPI thin films were dried for 12 hr in a desiccator.
2-4. Proton Conductivity Measurement of ASPI Thin Films
The proton conductivity of thin films was obtained by impedance
analyzer and dielectric
interface system (SI1260 and SI1296; Solartron Analytical).
Impedance data were
collected in the frequency range between 10 MHz and 1 Hz with
amplitude of 50 mV. A
humidity-controlled and temperature-controlled chamber (SH-221;
Espec Corp.) was
used for a relative humidity (RH) range of 40–95% at 298 K. The
direction of impedance
measurement was taken parallel to the substrate (in-plane
direction). The gold electrodes
were prepared at two parallel edges of thin film by the gold
paste. Each impedance value
was plotted after the obtained semi-circle did not change in
each humidity. Proton
conductivity (σ) was calculated as following definition,
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11
Rltd
=σ , (1)
where R denotes the resistance value from impedance, l and t
stand for the contact
electrode length and the film thickness, respectively, and d
represents the distance
between the gold electrodes.
2-5. Water Uptake Measurements
Water uptake was measured using an in-situ QCM system. QCM
substrates were
connected to an oscillation circuit with a DC power supply and a
frequency counter
(53131A; Agilent Technologies Japan Ltd.). The QCM substrate was
placed in an in-
house constructed humidity chamber with a high-resolution RH
sensor. Various humidity
environments were produced using dry N2 and humidified streams
applied by a humidity
controller (BEL Flow; BEL Japan Inc.). The frequencies before
and after spin-coating of
the QCM substrate were confirmed at the dry N2 stream for
determination of the mass of
dry film using the Sauerbrey equation
Δm = 𝑆𝑆×�𝜌𝜌𝜌𝜌2×𝐹𝐹2
× (−Δ𝐹𝐹) , (2)
where S represents the electrode surface area, ρ and µ denote
the quartz density and quartz
shear modulus, and F stands for the fundamental frequency of QCM
substrate.
The water content λ was calculated as
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12
λ = � 𝑚𝑚𝑚𝑚0
− 1� × 𝐸𝐸𝐸𝐸𝑀𝑀𝐻𝐻2𝑂𝑂
, (3)
where m signifies the film mass at each RH, m0 stands for the
film mass at the 0%RH,
MH2O denotes the molecular mass of water molecular, and EW
expresses the equivalent
weight of each ASPI.
2-6. Polarized Optical Microscopy (POM)
POM was used to elucidate the lyotropic LC-like domain
morphologies and their size in
ASPI films. The POM observations were taken using an optical
microscope (BX51,
BX51-P; Olympus Corp.) with a digital camera (DP28 camera;
Olympus Corp.) All POM
observations were conducted at room temperature and ambient
humidity.
2-7. Grazing-Incidence Small-Angle X-ray Scattering
(GI-SAXS)
Measurements
In-situ GI-SAXS was performed on a X-ray diffractometer (FR-E;
Rigaku Corp.) with an
R-AXIS IV two-dimensional detector. The thin film sample was
placed into the humidity-
controlled cell on the goniometer and vertical stage
(ATS-C316-EM/ALV-300-HM; Chuo
Precision Industrial Co. Ltd.). The humidified cell holds Kapton
windows. To control the
humidity nitrogen gas was used from the gas cylinder without
further dehumidification.
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13
Wavelength and beam size of X-ray were λ = 0.1542 nm by Cu Kα
radiation and
approximately 300 μm × 300 μm, respectively. The camera length
was 300 mm and the
incidence angle was set in the range of 0.20° to 0.22°.
2-8. Infrared p-polarized Multiple-angle Incidence
Resolution
Spectrometry (pMAIRS)
pMAIRS which was developed by Hasegawa51-54 was carried out to
identfy IP and OP
molecular vibrations in an identical thin film. An FT-IR
spectrometer (Nicolet 6700;
Thermo Fisher Scientific Inc.) was used for pMAIRS measurements
equipped with a
mercury–cadmium–telluride (MCT) detector. P-polarized light was
used by a ZnSe
polarizer. The angles of incidence for single-beam spectra were
taken from 38° through
8° in 6° steps. The wavenumber resolution and number of scans
were 4 cm-1 and 64 times
for each incident angle, respectively. Dry air or N2 gases were
purged through the sample
compartment and inside of the spectrometer to achieve less than
5% for humidity
condition. The aperture was fully opened to obtain wide range
beam size. A metal plate
with small pore arrays was placed in the light path to avoid the
light saturation for the
MCT detector. The pMAIRS analysis from the angular dependent
spectra was conducted
automatically using pMAIRS analyzer software (Thermo Fisher
Scientific Inc.).
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14
3. Results and Discussion
3-1. Proton Conductivity and Water Uptake
The proton conductivity of the planar ASPI-1, ASPI-2, bent
ASPI-3, and ASPI-4 thin
films for various RH at 298 K is presented in Figure 1. Proton
conductivity of all ASPI
thin films increased exponentially with RH, which is a typical
phenomenon of proton
conductive polymers. Proton conductivity for all ASPI thin films
showed a remarkably
higher value above 10-2 S / cm (at 25°C, 95% RH). This value is
higher than that of 400-
nm-thick Nafion thin film,18 which indicates that not only
planar ASPI but also bent ASPI
thin films can exhibit high proton conductivity as a form of
thin film.
The water uptake of the polymer electrolyte membrane is an
important factor for the
proton conductivity. The RH dependence of water uptake of planar
ASPI-1, ASPI-2, bent
ASPI-3, and ASPI-4 thin films was investigated for hydration
behavior using in-situ QCM
measurements. The obtained data are presented in Table 1. Figure
S4 presents the
humidity dependence of the number of water molecules per
sulfonic acid (λ [H2O /
SO3H]). All ASPI thin films showed similar curves for water
uptake.
As presented in Figure 2, the proton conductivity of the planar
ASPI-1 and ASPI-2
exhibits more than two times higher conductivity than that of
the bent ASPI-3 and ASPI-
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15
4 in the high water uptake condition. An earlier study
demonstrated that the degree of
molecular ordering strongly affects proton conductivity.24 To
reveal the origin for the high
proton conductivity in both planar and bent ASPI thin films,
POM, GISAXS, pMAIR
measurements were carried out.
Figure 1. Proton conductivity of the ASPI-1 (IEC = 2.89), ASPI-2
(IEC = 3.11), ASPI-3 (IEC = 2.72), and ASPI-4 (IEC = 2.78) thin
films as a function of relative humidity at 298 K.
Table 1. Physical Properties of ASPI thin films.
Sample IEC (mequiv/g) Mw H+ conductivityc
(S/cm)
Water uptaked (%) λd
ASPI-1 2.89a 4.9 × 105 1.78 × 10-1 76.8 14.8
-5
-4
-3
-2
-1
0
40 50 60 70 80 90 100
ASPI-1 (2.89)ASPI-2 (3.11)ASPI-3 (2.72)ASPI-4 (2.78)
RH / %
Logσ
/
S cm
-1
298 K
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16
(2.86)b
ASPI-2 3.11 a
(3.08) b 8.0 × 105 1.96 × 10-1 78.7 14.0
ASPI-3 2.72 a
(2.69) b 6.5 × 105 0.29 × 10-1 63.3 12.9
ASPI-4 2.78 a
(2.75) b 5.6 × 105 0.80 × 10-1 66.0 13.3
a Calculated from chemical structure. b Calculated from 1H NMR
results. c Proton conductivity, d water
uptake, and λ were measured at 95% RH.
0
0.05
0.10
0.15
0.20
2 4 6 8 10 12 14 16
ASPI-1ASPI-2ASPI-3ASPI-4
Water content λ[H2O/ SO
3H]
σ /
S
cm-1
Figure 2. Proton conductivity of the ASPI thin films as a
function of the λ value.
3-2. Morphology
Figure 3 portrays representative POM images of the planar
ASPI-1, ASPI-2, bent ASPI-
3, and ASPI-4 thin films. All ASPI films exhibited strong
birefringence, which can be
attributed to LC-like morphology. Our previous study revealed
that the molecular weight
of polymer affects the LC optical domain size24 Therefore in
this study, similar molecular
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17
weight (Table 1) was chosen for planar and bent ASPIs for
comparison. Results suggest
that the LC-like morphology and domain size depend not only on
the molecular weight
but also the polymer backbone. Differences of the morphology and
domain size can affect
the internal nanostructure. Therefore, detailed structural
analysis was conducted using
GI-SAXS measurements.
Figure 3. Polarized optical microscope image of the ASPI thin
films: (a) ASPI-1, (b) ASPI-2, (c) ASPI-3, and (d) ASPI-4
3-3. GI-SAXS
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18
To investigate the molecular ordered structure at the various
humidity conditions, in-situ
GI-SAXS measurements were taken for planar ASPI-1, ASPI-2, bent
ASPI-3, and ASPI-
4 thin films. Figure 4 portrays 2D GI-SAXS patterns at 0 and 95%
RH and λ value
dependent 1D GI-SAXS profiles in the in-plane (IP) and
out-of-plane (OP) directions. In
our previous study of the GI-SAXS measurements (Figure 4b), a
self-assembled lamellar
structure parallel to the substrate surface has been determined
in the planar ASPI-2 thin
film.22,24 This lamellar distance expands linearly to the
out-of-plane direction by water
uptake. Furthermore, molecular ordering improves by water uptake
based on the lyotropic
LC property (Figure S5). In the in-plane direction, an uptaken
water insensitive scattering
peak (qy = 0.38 Å-1) is visible, which is attributable to the
periodic monomer unit length.
The planar ASPI-1 (Figure 4a), bent ASPI-3 (Figure 4c), and
ASPI-4 (Figure 4d) thin
films exhibit a similar humidity-dependent self-assembly
structure. The d-spacing and
assignment of the peaks are presented in Table 2. Figures 5 and
6 respectively depict
similar behavior for enhancement of the molecular ordering and
linear expansion of
lamellar structure by water uptake, which is visible for all
ASPI thin films. In the planar
structure of ASPI-1, π-stacking at qy = 1.75 Å-1 (d = 0.35 nm)
was observed because of
the strong interaction of the aromatic ring. This scattering
peak was enhanced by water
uptake.
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19
In the in-plane direction at qy = 0.38 Å-1 (d=1.63 nm), the peak
for periodic monomer
unit length of the polyimide main chain was observed only in the
planar-backbone ASPI-
1 and ASPI-2 thin films. This value was found to be close to the
periodic unit length
estimated from DFT calculation. In the cases of the bent ASPI-3
and ASPI-4 thin films,
no apparent scattering peak by the periodic monomer unit length
was observed. Therefore
main chain orderings of the bent ASPI-3 and ASPI-4 parallel to
the surface direction are
lower than those of the planar ASPI-1 and ASPI-2 thin films.
Nevertheless, uptaken water
sensitive peaks in the out-of-plane direction were observed as a
lamellar structure,
indicating a humidity-induced lyotropic lamellar structure
parallel to the substrate plane.
Ando et al. assessed the molecular aggregation structures of
polyimides with both
aromatic planar and bent molecular structures using GI-SAXS
analysis.50 The aromatic
polyimide chains with nonplanar and bent molecular structure are
packed laterally along
the in-plane direction in ordered domains. However, the degree
of molecular ordering in
the bent polyimide is weaker than that in the planar polyimide.
In the case of ASPI, the
amphiphilic polyimide with alkyl sulfonated side chains can
promote the organization of
the lamellar structure with in-plane orientation because of the
lyotropic LC property.
Results obtained using GI-SAXS revealed that both planar and
bent polymer thin films
formed an in-plane oriented lamellar structure in which the
lamellar distance expanded to
-
20
the out-of-plane direction and the degree of molecular ordering
improved by water uptake.
Figure 4. The 2D GI-SAXS patterns at 0%RH and 95%RH
respectively, and 1D GI-SAXS profiles in the in-plane and
out-of-plane directions as a function of the λ value of the (a)
ASPI-1, (b) ASPI-2, (c) ASPI-3, and (d) ASPI-4 thin films.
Scattering arcs at the positions of qy = 0.75 and 0.82 Å-1 were
originated by diffraction from the window material for the
humidity-controlled cell.
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21
Table 2. d-Spacing and assignment in the in-plane (IP) and
out-of-plane (OP) directions
Sample Direction d-spacing / nm
Assignment 0% RH 95% RH
ASPI-1 OP 1.3 2.85 lamellar
OP ― 0.35 π-stack
IP 1.6 1.6 (001)
Monomer unit length
ASPI-2 OP 1.6 3.0 lamellar
OP 0.44 0.44 ch-pack
IP 1.6 1.6 (001)
Monomer unit length
ASPI-3 OP 1.66 3.08 lamellar
OP 0.56 0.58 ch-pack
ASPI-4 OP 1.52 2.94 lamellar
OP 0.42 0.42 ch-pack
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22
0
2 103
4 103
6 103
8 103
1 104
0 2 4 6 8 10 12 14 16
ASPI-1ASPI-2ASPI-3ASPI-4
Inte
nsity
/ cp
s
Water content λ[H2O/ SO
3H]
Figure 5. Scattering intensity of the lamellar structure for
ASPI-1, ASPI-2, ASPI-3, and ASPI-4 thin films as a function of the
λ value.
Figure 6. Lamellar distance (Δd-value) as function of the λ
value of the ASPI thin films.
0
0.5
1.0
1.5
0 2 4 6 8 10 12 14 16
ASPI-1ASPI-2ASPI-3ASPI-4
Water content λ[H2O/ SO3H]
Lam
ella
r dis
tanc
e / n
m
-
23
3-4. pMAIRS
Infrared p-polarized multiple-angle incidence resolution
spectrometry (pMAIRS) was
applied to the ASPI thin films to ascertain the orientation of
the main chain. IR pMAIRS
is increasingly regarded as a powerful spectroscopic tool for
investigating molecular
orientation in thin films.51–54 Figure 7 presents pMAIR spectra
of the planar ASPI-1,
ASPI-2, bent ASPI-3, and ASPI-4 thin films. The observed
vibrational modes at 1380 and
1500 cm –1 except ASPI-1 are assigned respectively to the C–N
bonds of the main chain
and to phenyl C–C stretching vibration. Adjacent vibrational
modes at 1720 and 1780 cm–
1 respectively correspond to the C=O asymmetric and symmetric
stretching vibrations of
imide groups. In a similar manner, pMAIR spectrum of the planar
ASPI-1 shows the C–
N bonds, C–C stretching vibration, and C=O asymmetric and
symmetric stretching
vibrations observed respectively at 1350, 1500, 1680, and 1720
cm–1.
The degree of molecular orientation is calculable from in-plane
and out-of-plane
absorbance for each functional group.54 A large difference
between IP and OP absorbance
reflects the anisotropic orientation of the molecular structure.
All thin films gave stronger
absorbance in the IP spectrum than in the OP spectrum at C=O
symmetric and C–N
stretching vibrational modes. These vibrational modes correspond
to the main chain
orientation parallel to the substrate surface. No large
differences in molecular orientation
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24
among all ASPI thin films has been confirmed. Both pMAIR and
GI-SAXS results show
good consistency for in-plane orientated structures of main
chains.
Figure 7. pMAIR spectra of the (a) ASPI-1, (b) ASPI-2, (c)
ASPI-3, and (d) ASPI-4 thin films. 3-5. Planar and Bent ASPI Thin
Films
From structural analyses conducted using both pMAIRS and
GI-SAXS, we propose the
organized lamellar structure with highly in-plane ordering
structure for high proton
conduction as shown in Figure 8. All ASPI thin films enhance the
molecular ordering with
expansion of lamellar structure to the out-of-plane direction by
water uptake. Amphiphilic
polyimides with alkyl sulfonated side chains drive the organized
lamellar structure with
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25
the in-plane orientation. Results indicate that not only planar
but also bent polymer
backbones of the ASPI thin films exhibit high proton conductive
channels because of the
lyotropic LC property. In-situ FT-IR results in Figure S6 and S7
reveal that dissociation
state of proton at sulfonic acid groups is identical in all ASPI
thin films. The difference
of proton conductivity between the planar and bent ASPI thin
films can be derived from
the degree of molecular ordering. Smectic ordering of main
chains in ASPI-1 and ASPI-
2 thin films can enhance the water uptake in the high RH region
and can enable exhibition
of higher proton conductivity.
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26
Figure 8. Proposed organized lamellar structure with a highly
in-plane ordered structure of both planar and bent polymer
backbones.
4. Conclusion
Understanding the relation between structure and proton
transport property is
fundamentally important to develop high proton conductive
materials. In earlier studies,
interchain packing for the organized lamellar structure was
suppressed by steric effects
of nonplanar and bent backbones of polyimides. This study
provides a new perspective
of the organized lamellar structure using lyotropic LC property
by alkyl sulfonated groups
at the side chain. Our results indicate that amphiphilic
polyimides with alkyl sulfonated
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27
side chains drive the organized lamellar structure with in-plane
orientation in both planar
and bent backbones. These organized lamellar structures of the
in-plane oriented ASPI
thin films achieve high proton conductivity exceeding 10-2 S/cm.
The degree of the
molecular ordering of those hydrated domains increased with
water uptake. Results
obtained through this study extend the molecular design for high
proton conductive
polymers with humidity-induced lyotropic LC property.
Acknowledgments
This work was supported in part by the Nanotechnology Platform
Program (Molecule and
Material Synthesis) of the Ministry of Education, Culture,
Sports, Science and
Technology (MEXT), Japan. This work was partially supported by
Iketani Science and
Technology Foundation (ISTF), JAPAN.
Supporting information
Synthesis and characterization of sulfonated polyimide, 1H NMR
spectra, FT-IR spectra,
water solubility test, mechanical test, water uptake, in-situ
FT-IR spectra, and temperature
dependence of proton conductivity.
Author information
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28
Corresponding author
*[email protected] Phone: +81(Japan)-761-51-1541, Fax:
+81(Japan)-761-51-1149,
Address: 1-1 Asahidai, Nomi, Ishikawa 923-1292, Japan
Notes
The authors have no financial conflict of interest to
declare.
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